In:
International Journal of Chemical Kinetics, Wiley, Vol. 53, No. 6 ( 2021-06), p. 702-715
Abstract:
Vibrational excitation of the H 2 O, HOD, and D 2 O product molecules from the reactions of OH and OD radicals with CH 3 SH, CH 3 C(O)SH, (CH 3 ) 3 CSH, H 2 S, and CH 3 SCH 3 was determined by modeling the infrared emission spectra using a renovated and extended set of model spectroscopic bands. Using the deuterated reactant, CH 3 SD, it was possible to separate spectra of abstraction from C‐ and S‐sites, which allowed measurement of branching fractions and kinetic isotope effects for individual channels. For the OH + CH 3 SH reaction, branching fractions of 0.13 ± 0.03 (C─H) and 0.87 ± 0.03 (S─H) were obtained. The vibrational energy released to water from abstraction of H‐atoms from the C─H and S─H sites of the reactant molecules is described. The results reported in this paper take precedence over an earlier study of CH 3 SH. The vibrational energy partitioning between the stretch and bend modes of water molecules from the reactions of the thiols and related reactions of H 2 S and CH 3 SCH 3 are discussed. The mechanism for the OH + CH 3 SSCH 3 reaction was confirmed to be addition followed mainly by decomposition to CH 3 SH and CH 3 SO.
Type of Medium:
Online Resource
ISSN:
0538-8066
,
1097-4601
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
1480875-4
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